Preparation of substitute resin oils



Patented Apr. 12, 1938 UNITED STATES PATENT OFFICE WHICH ARE DERIVED FROM THE BY- PRODUCTS F PETROLEUIVI REFINING Arthurv Lazar, Associated, Calif., assignor, by mesne assignments, to Tide Water Associated Oil Company, a corporation of Delaware No Drawing. Application April 30, 1934, Serial No. 723,168

10 Claims.

This invention is directed to the preparation of substitute resin ,oils which are derived from the by-products of petroleum refining;

The principal object of the invention is to convert the by-products from refining petroleum with selective solvents such as liquid sulphur dioxide, 'dichlorcthyl ether, phenol, nitrobenzene, iurfural, and others to obtain resin oil substitutes.

Another object is to convert such by-products.

to obtain resin oil substitutes and a valuable emulsifying agent.

In treating petroleum, or its distillates, with Such selective solvents, the solvents take up cer- 5 tain hydrocarbons which may generally be termed unsaturated and aromatic hydrocarbons and which, when in solution, are removed as an extract from the main body of oil under treatment. 4

Treatment with sulphuric acid in the usual way will not change these conditions to any marked degree, because in order to obtain any appreciable 3c efiect as to decolorizing and color stability such tremendous quantities of sulphuric acid must be used that a large portion of the extract will be converted into valueless acid sludge. Even when such a Severe acid treatment is given the extract,

: the oil remaining after removal of acid sludge does not show features desirable for use in the many applications which this invention now provides.

In order to purify the extract to obtain lighter and permanent color, it is found that such may be accomplished in general by distilling the Same,

preferably under a high vacuum and with direct steam, in the presence of an alkaline material,

Such as caustic soda, potassium hydroxide, hy-

drated lime, magnesium oxide, and barium hydroxide, all of whichexercise substantially the same function and any of which may be used in the solid, or solution form.

There are two ways which lead to a final distillation step, either of which maybe used to obtain the desired results.

The first method consists in agitating the alkaline reagent with the extract, then removing the excess alkali together with whatever precipitate that may have been formed and distilling the treated extract in the usual manner to obtain a condensate, or the extract may be distilled under high vacuum with direct steam without removal of the alkaline material to leave from 10% to 20% of bottoms.

In the event that such excess alkali and precipitate is removed there will be no alkali dissolved in the oil when the original extract contains no organic acidic compounds, such as naphthenic acids, but any alkali contained therein will be in suspension.

However, if the original extract, or original distillate from which such extract is derived contains such organic acidic compounds, the tendency is to form oil soluble organic salts or Soaps.

In either event like valuable products are obtained to be used as resin oil substitutes but the bottoms after redistillation have difierent properties; the bottoms from an extract containing organic acidic compounds cont'ain valuable oil soluble soaps, such as soaps of naphthenic acid and Sulphonated naphthenic acids which have a pronounced emulsifying efiect in contact with water, or impart such emulsifying effects when added to ordinary mineral oils.

On the other hand, the bottoms from an extract containing no organic acidic compounds will be free from soaps and contain largely mineral salts which do not have this emulsifying property.

The second method consists in treating the extract with sulphuric acid in such quantity that it exercises no chemical effect on the oil itself, but just coagulates the resinous bodies. The point at which the coagulation of the resinous bodies is complete and a further addition of acid would have a noticeable chemical effect on the oil itself is indicated by a liberation of S02 gas during the agitation. The amount of sulphuric acid necessary and the strength of the sulphuric acid which will bring about this desired efiect varies within certain limits. depending on the nature of the extract which again varies with the source of crude from which the oil originated. It has been found that acid rates can vary between one and ten pounds per barrel of extract and that the strength of sulphuric acid can vary between and 98%. The. variations in the nature of the extracts will be easily understood from the fact that the various solvents used for refining differ from each other quite considerably in their selectivity and that the crude distillates on which the Solvents are applied difier quite considerably in their composition.

The acid sludge is then separated from the oil which is neutralized by the ordinary use of adsorbent material, such as filtration through clay. Alternatively the acid treated extract, after sludge removal, may be distilled under high vacuum with direct steam in the presence of the alkaline material and the oil recovered as a desired condensate, leaving from 10% to 20% of bottoms. The effect of the alkaline reagents used is to insure a substantially complete removal of compounds of an acidic nature together with the destruction, or polymerization, of certain unstable compounds left in the oil. It would seem that the removal, or separation, of the above compounds removes the causes for restricted range in the use of the extract, insofar as the products of such a treatment show very light colors and excellent color stability,

Two specific examples of treating the extract, including the use of a small amount of sulphuric acid insufiicient to cause oxidation or sulphonation of the extracted hydrocarbons are herewith given, it being noted in one example that while there is no sulphonation of the hydrocarbons there is sulphonation of organic acids, such as naphthenic acids.

Example A imate range of viscosity between and 150 at- 210 F., is agitated for about one hour with concentrated sulphuric acid (98%) at atmospheric temperature, the acid being used at the rate of about 2 pounds of acid per barrel of extract.

The mixture is then permitted to settle for about twelve hours and the acid sludge is then removed. The acid treated extract is redistilled (preferably under vacuum) in the presence of from 0.8 to 1.0 pound of NaOH per barrel of the extract torecover the desired resin oil substitutes, which may be fractionated to yield a light resin oil substitute comprising about 10% of the charge, a medium resin oil substitute comprising about 40% of the charge and a heavy resin oil substitute comprising about 40% of the charge, thus leaving about 10% of bottoms. In this case the bottoms contain besides residual oily constituents an appreciable quantity of salts resulting from the neutralization of the acidity imparted to the oil during acid treatment, this neutralization being the main function of the use of the alkali. Said bottoms have no particular emulsifying action when mixed with water, or with further mineral oil and water.

Example B An extract containing unsaturated and aromatic hydrocarbons obtained fromtreating a California lubricating distillate, or any other lubricating crude, with liquid S01, containing organic acids and having an approximate range of viscosity between 40 and 150 at 210 F. is agitated for about one hour with concentrated sulphuric acid(98%) at atmospheric temperature, the acid being used at the rate of about 2 pounds of acid per barrel of extract. The mixture is then permitted to settle for about twelve hours and the acid sludge is then removed. The acid treated extract is redistilled (preferably under vacuum) in the presence of from 1.5 to 2 pounds of NaOH per barrel of extract to recover resin oil substitutes and bottoms in the same proportions as yielded from Example A, with the distinguishing diiference that the 10% bottoms left after redistillation in the present example contain besides residual oily constituents an appreciable quantity of oil soluble soaps of organic acids and of sulfonated organic acids together with the salts of whatever other products of acid nature which have been imparted to the oil by the action of the acid. The bottoms thus obtained from the treatment by Example B have valuable emulsifying properties with water and emulsions may be made therefrom by dispersal in desired volumes of water or by diluting with further mineral oil and dispersing the dilution in water.

The extract, or resin oil substitutes, processed as above described, shows excellent compatability with solvents like alcohol, acetone, esters and other'organic compounds, a property which ordinary mineral oil does not possess. Furthermore, the treated extract is a desirable plasticizer for nitrocellulose lacquers and enamels being of a non-drying viscous character and very stable in the presence of light.

The extract may also be used as a solvent for rubber, either alone, or mixed in any proportion with other rubber solvents, as a substitute for refined resin oils, and generally as a solvent for resins, gums, varnishes or asphalt.

Likewise, the extract has a wide field as a blending material with all vegetable oi1s,particularly castor oil, a property which ordinary hydrocarbon oils do not possess.

The physical characteristics of the treated extract closely resemble those of refined resin oils, as the tables below indicate, applicant's product being obtained from a distillate of a California crude, having the following characteristics and being treated in the following specific manner:

It will be noted that the evolution of S0: from the treatment with sulphuric acid is merely indicative of the amount of sulphuric acid which should be used, and the amount and concentration of the acid used is such as to cause substantially no oxidation or sulphonation of the extracted hydrocarbons.

This application is a continuation in part of my copending application Ser. No. 492,613, filed October 31, 1930.

I claim as my invention:

1. In a process of treating an extract obtained from hydrocarbon oils by selective solvents and consisting mainly of unsaturated and aromatic hydrocarbons of a boiling range higher than kerosene, agitating a body of such extract, derived from substantially uncracked petroleum, substantially freed from the solvent which extracted it and substantially free from saturated hydrocarbons, with from 1 to 10 pounds per barrel of sulphuric acid until sulphur dioxide commences to be given off, separating the acid sludge from said body, then distilling said body in the presence of an alkaline material; the amount, conditions of treatment, and concentration of the sulphuric acid used being insuflicient to cause.

oxidation or sulphonation of the said hydrocarbons but being sufficient to cause coagulation of undesired resin-forming bodies contained therein.

2. In a process of treating an extract obtained from hydrocarbon oils by selective solvents and consisting mainly of unsaturated and aromatic hydrocarbons of a boiling range higher than kerosene: agitating a body of such extract, derived from substantially uncracked petroleum, substantially freed from the solvent which extracted them and substantially free from saturated hydrocarbons, with from 1 to 10 pounds per barrel of sulphuric acid until sulphur dioxide commences to be given off, separating the acid sludge from said 'body, then distilling said body in the presence of an alkaline material to leave from 10% to 20% of bottoms; the amount, conditions of treatment, and concentration of the sulphuric acid used being insufiicient to cause oxidation or sulphonation of the said hydrocarbons but being sufficient to cause coagulation of undesired resinforming bodies contained therein.

3. In a process of treating an extract obtained from hydrocarbon oils by selective solvents and consisting mainly of unsaturated and aromatic hydrocarbons of a boiling range higher than kerosene: agitating a body of such extract, derived from substantially uncracked petroleum, substantially freed from the solvent which extracted it and substantially free from saturated hydrocarbons, with-from 1 to 10 pounds per barrel of concentrated sulphuric acid until sulphur dioxide commences to be given 01f, separating the acid sludge from said body, then distilling said body in the presence of an alkaline material; the amount and concentration of the sulphuric acid used being insufiicient to cause oxidation or sulphonation of the said hydrocarbons but being sufficient to cause coagulation of undesired resinforming bodies contained therein.

4. The process of preparing a resin oil substitute which comprises: treating a lubricating oil hydrocarbon stock with a selective solvent to extract a body of hydrocarbons consisting mainly of aromatic and unsaturated hydrocarbons, separating the solvent from said body, agitating said body with about two (2) pounds of concentrated sulphuric acid per barrel, removing the acid sludge, distilling the acid treated body in the presence of NaOH in the proportion of about from 0.8 to 1.0 pound of the alkali per barrel of said body, and recovering a condensate therefrom.

5. The process of preparing a resin oil substitute which comprises: treating a lubricating oil hydrocarbon stock with a selectivesolvent to extract a body of hydrocarbons consisting mainly of aromatic and unsaturated hydrocarbons, separating the solvent from said body, agitating said body with about two (2) pounds of concentrated sulphuric acid per barrel, removing the acid sludge, distilling the acid treated body in the presence of NaOH in the proportion of about from 1.5 to 2 pounds of the alkali per barrel of said body, recovering a condensate therefrom, and recovering unvolatilized bottoms soluble in a mineral oil.

6. The process of preparing a resin oil substitute which comprises treating a lubricating oil hydrocarbon stock with a selective solvent to extract a body of hydrocarbons consisting mainly of aromatic and unsaturated hydrocarbons, separating the solvent from said body, agitating said body with about two (2) pounds of concentrated sulphuric acid per barrel, removing the acid sludge, distilling the acid treated body in the presence of NaOH in the proportion of about from 1.5 to 2 pounds of the alkali per barrel of said body, and recovering about of said body as a condensate and about 10% as unvolatilized bottoms.

stitute which comprises: treating a lubricatingoil hydrocarbon stock with liquid S02 to extract a body of hydrocarbons consisting mainly of aromatic and unsaturated hydrocarbons, separating the solvent from said body, agitating said body with about two (2) pounds of concentrated sulphuric acid per barrel, removing the acid sludge, distilling the acid treated body in the presence of NaOH in the proportion of about from 0.8 to 1.0 pound of the alkali per barrel of said body, and recovering a condensate therefrom.

8. The process of preparing a solvent oil from petroleum which has characteristics similar to resin oil, which comprises: extracting a distillate heavier than kerosene and derived from substantially uncracked petroleum with a selective solvent to obtain a body of aromatic and unsaturated hydrocarbons containing polymerizable compounds, treating said extracted body with about from 1 to 10 pounds per barrel of sulphuric acid of from about 90% to 98%.'concentration, removing the acid sludge, distilling the thus treated oil in the presence of an alkaline material to cause polymerization of said compounds, and

recovering a condensate therefrom; said condensate being substantially free of said compounds and said selective solvent, and having a specific gravity not lower than about 0.965.

9. A process of preparing a solvent oilfrom petroleum which has characteristics similar to resin oil, which comprises: treating anuncracked petroleum oil of a boiling ranger higher than kerosene with a selective solvent to extract a 7. The process of preparing a resin oil subbody of hydrocarbons mainly of an unsaturated and aromatic nature, removing the solvent from said body and distilling said body in the presence of an alkaline material, and recovering a condensate therefrom having a specific gravity not lower than about 0.965.

10. A process of preparing a solvent oil from i petroleum which has characteristics similar to resin oil, which comprises: treating an uncracked petroleum oil of a boiling range higher than kerosene with liquid sulphur dioxide to extract a body of hydrocarbons mainly of an unsaturated and aromatic nature, removing the solvent from said body and distilling said body in the presence of' an alkaline material, and recovering a condensate therefrom having a specific gravity not lower than about 0.965.

ARTHUR LAZAR; 

